JP3166787U - Adhesive rubber sheet for human body decoration - Google Patents

Abstract

The present invention can be used for a long time without lowering the adhesive strength, and can be re-applied even if peeled off, enables repeated use, and is effectively used for decoration of skin, nails and the like. To provide an adhesive rubber sheet for human body decoration. An adhesive layer made of an adhesive silicone resin or gel is formed on a base rubber layer. The base rubber is formed from a silicone rubber having a JIS-A hardness of 10 to 90. [Selection diagram] Fig. 1

Description

  The present invention relates to a pressure-sensitive adhesive rubber sheet for human body decoration that is directly attached to a human body such as human skin and nails for decoration.

Conventionally, various types of adhesive rubber sheets for human body decoration such as nail sheets have been proposed, but conventional rubber sheets such as nail sheets are inferior in re-pasteability and have problems in terms of reworkability. It was.
In addition, the following is mentioned as a prior art relevant to this invention.

JP 11-319065 A JP 2006-16368 A

  The present invention has been made in view of the above circumstances, can be used without causing a decrease in adhesive strength over a long period of time, and can be re-applied even after peeling, enabling repeated use, An object of the present invention is to provide an adhesive rubber sheet for human body decoration that is effectively used for decoration such as nails.

In order to achieve the above object, the present invention provides the following adhesive rubber sheet for human body decoration.
Claim 1:
A pressure-sensitive adhesive rubber sheet for decorating a human body, wherein a pressure-sensitive adhesive layer made of a pressure-sensitive silicone resin or gel is formed on a base rubber layer.
Claim 2:
The adhesive rubber sheet according to claim 1, wherein the base rubber is formed from a silicone rubber having a hardness of JIS-A of 10 to 90.
Claim 3:
The adhesive layer is (A) an organopolysiloxane containing an alkenyl group bonded to at least two silicon atoms in one molecule: 10 to 75 parts by mass,
(B) R ₃ SiO _1/2 unit (wherein R is an unsubstituted or substituted monovalent hydrocarbon group) and SiO ₂ unit as main components, and the moles of R ₃ SiO _1/2 unit and SiO ₂ unit A resinous material in which the ratio [R ₃ SiO _1/2 / SiO ₂ ] is 0.5 to 1.5 and R does not contain an alkenyl group or the total amount is less than 0.0001 mol / g. Polymer: 20 to 70 parts by mass,
(C) R ′ ₃ SiO _1/2 unit (wherein R ′ is an unsubstituted or substituted monovalent hydrocarbon group) and SiO ₂ unit as main components, R ′ ₃ SiO _1/2 unit and SiO ₂ unit And the molar ratio [R ′ ₃ SiO _1/2 / SiO ₂ ] is 0.5 to 1.5, R ′ contains an alkenyl group, and the total amount thereof is 0.0001 mol / g or more. Combined: 5-50 parts by mass,
(D) Organohydrogenpolysiloxane containing at least two hydrogen atoms bonded to silicon atoms in one molecule: 0.5 to 30 with respect to 100 parts by mass in total of components (A), (B) and (C) The amount of hydrogen atoms bonded to the silicon atoms in the component (D) relative to the alkenyl groups bonded to the silicon atoms contained in the components (A), (B), and (C) is 0 parts by molar ratio. An amount of 32 to 0.75,
(E) Addition reaction catalyst: The adhesive rubber according to claim 1 or 2, wherein the cured product is formed from a cured product of an addition-curable silicone rubber composition having a surface adhesiveness, the catalyst containing a catalytic amount. Sheet.
Claim 4:
The adhesive rubber sheet according to any one of claims 1 to 3, wherein the adhesive layer has a hardness lower than that of the base rubber and an Asker C hardness of 1 to 60.
Claim 5:
The adhesive rubber sheet according to any one of claims 1 to 4, wherein the adhesive force of the adhesive layer to glass is 0.5 to 10 N / 25 mm.
Claim 6:
The adhesive rubber sheet according to any one of claims 1 to 5, wherein the base rubber has a thickness of 0.05 to 1 mm, and the adhesive layer has a thickness of 0.1 to 2 mm.
Claim 7:
It is a nail sheet, The adhesive rubber sheet of any one of Claims 1-6.
Claim 8:
The pressure-sensitive adhesive rubber sheet according to any one of claims 1 to 6, which is a cheering face or an arm sticking sheet.

  The pressure-sensitive adhesive rubber sheet of the present invention does not decrease in adhesive force over a long period of time, and can be reused without decreasing the adhesive force even if it is peeled off. Moreover, it can be affixed to a human body and can be used effectively for decorative sheets such as skin and nails. Furthermore, since it has elasticity, it can follow the surface of the human body and can provide a sheet with little damage.

It is sectional drawing which shows one Example of this invention. It is a perspective view which shows the example at the time of using the adhesive rubber sheet of this invention as a nail seal. It is a perspective view which shows the example which affixed the adhesive rubber sheet of this invention on the face part as a cheering seal.

  As shown in FIG. 1, an adhesive rubber sheet 10 of the present invention is formed by laminating an adhesive layer 2 on one side of a base rubber 1, and a cover film 3 is usually laminated on the adhesive layer 2 in a peelable manner. In use, the cover film 3 is peeled off, and the adhesive layer 2 is adhered to the required place.

  Here, as a rubber base | substrate which comprises the said base rubber, a silicone rubber is preferable from the point which has elasticity, a weather resistance, and transparency. The silicone rubber is not particularly limited, and any silicone rubber obtained by curing a conventionally known silicone rubber composition may be used, but a JIS-A hardness measured by a durometer A hardness meter defined in JIS K 6249. It is preferable in terms of elasticity and rubber strength to use a silicone rubber having a thickness of 10 to 90, more preferably 20 to 80, still more preferably 25 to 75. When the JIS-A hardness is less than 10, the strength as rubber may be inferior, and when it exceeds 90, the elasticity may be inferior.

  The silicone rubber composition may be of any curable type, but addition (hydrosilylation) reaction curable type silicone rubber composition or organic peroxide curable type silicone from the point that molding can be done in a short time by heating. Those obtained from the rubber composition are preferred. This addition reaction curable silicone rubber composition may be of a known composition, an alkenyl group-containing organopolysiloxane having two or more alkenyl groups represented by vinyl groups in one molecule, and two or more SiH groups. , Preferably 3 or more organohydrogenpolysiloxanes (usually in an amount such that the molar ratio of SiH groups to alkenyl groups is 0.5 to 4) and platinum group metal-based addition reaction catalysts represented by platinum compounds (Normally, 1 to 1,000 ppm relative to the alkenyl group-containing organopolysiloxane) is used. Further, the organic peroxide curable silicone rubber composition may be of a known composition, preferably an effective amount of organic peroxide as a curing agent in organopolysiloxane having two or more alkenyl groups in one molecule. What is blended (usually 1 to 10 parts by mass with respect to 100 parts by mass of the organopolysiloxane) is used.

  Commercially available products can be used as the silicone rubber composition. For example, as an addition reaction curable silicone rubber composition, KE-1935A / B, KE-1950-60A / B, KEG-2000- manufactured by Shin-Etsu Chemical Co., Ltd. 40A / B and the like are organic peroxide curable silicone rubber compositions such as KE-551-U, KE-571-U, KE-1571-U, and KE-951-U manufactured by Shin-Etsu Chemical Co., Ltd. Used.

  The pressure-sensitive adhesive layer is composed of a silicone resin or gel having adhesiveness, and in particular, an addition-curable composition is used in combination with a silicone resin that imparts adhesiveness and a silicone resin that imparts rubber strength. Thus, while having a certain rubber hardness and rubber strength, it is possible to have adhesiveness that can be adhered and fixed to a base material or various parts.

Here, as the adhesive layer,
(A) Organopolysiloxane containing an alkenyl group bonded to at least two silicon atoms in one molecule: 10 to 75 parts by mass
(B) R ₃ SiO _1/2 unit (wherein R is an unsubstituted or substituted monovalent hydrocarbon group) and SiO ₂ unit as main components, and the moles of R ₃ SiO _1/2 unit and SiO ₂ unit A resinous material in which the ratio [R ₃ SiO _1/2 / SiO ₂ ] is 0.5 to 1.5 and R does not contain an alkenyl group or the total amount is less than 0.0001 mol / g. Polymer: 20 to 70 parts by mass,
(C) R ′ ₃ SiO _1/2 unit (wherein R ′ is an unsubstituted or substituted monovalent hydrocarbon group) and SiO ₂ unit as main components, R ′ ₃ SiO _1/2 unit and SiO ₂ unit And the molar ratio [R ′ ₃ SiO _1/2 / SiO ₂ ] is 0.5 to 1.5, R ′ contains an alkenyl group, and the total amount thereof is 0.0001 mol / g or more. Combined: 5-50 parts by mass,
(D) Organohydrogenpolysiloxane containing at least two hydrogen atoms bonded to silicon atoms in one molecule: 0.5 to 30 with respect to 100 parts by mass in total of components (A), (B) and (C) The amount of hydrogen atoms bonded to the silicon atoms in the component (D) relative to the alkenyl groups bonded to the silicon atoms contained in the components (A), (B), and (C) is 0 parts by molar ratio. An amount of 32 to 0.75,
(E) Addition reaction catalyst: It is preferably formed from a cured product of an addition-curable silicone rubber composition containing a catalytic amount, and the cured product having surface tackiness.

The component (A) of the addition curable silicone rubber composition is an organopolysiloxane having at least two alkenyl groups on average in one molecule, and the organopolysiloxane of the component (A) includes the following average composition formula: (1)
R ¹ _a SiO _{(4-a) / 2} (1)
What is shown by is used.

In the formula, R ¹ is an unsubstituted or substituted monovalent hydrocarbon group having the same or different carbon number of 1 to 10, preferably 1 to 8, and a is 1.5 to 2.8, preferably 1.8. It is a positive number in the range of ˜2.5, more preferably 1.95 to 2.05. Here, as the unsubstituted or substituted monovalent hydrocarbon group bonded to the silicon atom represented by R ¹ , a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, Pentyl group, neopentyl group, hexyl group, cyclohexyl group, octyl group, nonyl group, alkyl group such as decyl group, aryl group such as phenyl group, tolyl group, xylyl group, naphthyl group, benzyl group, phenylethyl group, phenylpropyl Aralkyl groups such as groups, vinyl groups, allyl groups, propenyl groups, isopropenyl groups, butenyl groups, hexenyl groups, cyclohexenyl groups, octenyl groups and other alkenyl groups, and some or all of the hydrogen atoms of these groups are fluorine. Substituted with halogen atoms such as bromine, chlorine, cyano groups, etc., such as chloromethyl group, chloropro Group, bromoethyl group, trifluoropropyl group, but cyanoethyl group and the like, Preferably, at least 90 mol% of all R ¹ is a methyl group.

In this case, at least two of R ¹ must be alkenyl groups (preferably having 2 to 8 carbon atoms, more preferably 2 to 6). The content of the alkenyl group is 0.0001 to 20 mol%, preferably 0.001 to 10 mol%, particularly in the total organic group (that is, the above-mentioned unsubstituted or substituted monovalent hydrocarbon group) R ^1. It is preferable to set it as 0.01-5 mol%. This alkenyl group may be bonded to a silicon atom at the end of the molecular chain, or may be bonded to a silicon atom in the middle of the molecular chain, or may be bonded to both. Those containing bonded alkenyl groups are preferred.

The degree of polymerization is not particularly limited and can be from liquid to raw rubber at normal temperature. Usually, the average degree of polymerization in terms of polystyrene by gel permeation chromatography (GPC) is 50 to 20,000, preferably 100. Those having a molecular weight of about 10,000 to 10,000, more preferably about 100 to 2,000 are preferably used.
The structure of this organopolysiloxane is basically composed of a repeating main chain consisting of diorganosiloxane units (R ¹ ₂ SiO _2/2 ), and both ends of the molecular chain are triorganosiloxy groups (R ¹ ₃ SiO _{1 / 2} ) or a linear structure blocked with a hydroxydiorganosiloxy group ((HO) R ¹ ₂ SiO _1/2 ), but may be partially a branched structure, a cyclic structure, or the like.

The resinous copolymer (that is, a copolymer having a three-dimensional network structure) as the component (B) has R ₃ SiO _1/2 units and SiO ₂ units as main components. Here, R is an unsubstituted or substituted monovalent hydrocarbon group, preferably having 1 to 10 carbon atoms, particularly 1 to 8 carbon atoms. Examples of the monovalent hydrocarbon group represented by R include a methyl group and an ethyl group. Propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, cyclohexyl group, octyl group, alkyl group such as nonyl group, decyl group, phenyl group, tolyl group, xylyl Group, aryl group such as naphthyl group, aralkyl group such as benzyl group, phenylethyl group, phenylpropyl group, vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, hexenyl group, cyclohexenyl group, octenyl group, etc. Or some or all of the hydrogen atoms of these groups are substituted with halogen atoms such as fluorine, bromine and chlorine, cyano groups, etc. Those conversion, such as chloromethyl group, chloropropyl group, bromoethyl group, trifluoropropyl group, cyanoethyl group and the like.

The resinous copolymer of the component (B) may be composed of only the R ₃ SiO _1/2 unit and the SiO ₂ unit, and if necessary, the R ₂ SiO unit or the RSiO _3/2 unit ( R may contain 50% or less, preferably 40% or less, based on the total copolymer mass, as a total amount of these as described above, but R ₃ SiO _1/2 units and SiO ₂ units The molar ratio [R ₃ SiO _1/2 / SiO ₂ ] is preferably 0.5 to 1.5, particularly preferably 0.5 to 1.3. Even if this molar ratio is smaller than 0.5 or larger than 1.5, the tackiness is lowered. Furthermore, the resinous copolymer of component (B) has an alkenyl group content of less than 0.0001 mol / g (that is, 0 to 0.0001 mol / g), preferably 0.00005 mol / g or less ( That is, it is 0-0.00005 mol / g), More preferably, it does not contain an alkenyl group. If the alkenyl group is contained in an amount of more than 0.0001 mol / g, sufficient adhesive strength cannot be obtained.
The resinous copolymer may be a liquid that is fluid at room temperature (for example, 25 ° C.) or a solid that is not fluid. However, the resinous copolymer may be solid at room temperature in terms of stickiness of the cured product. preferable. This resinous copolymer can be usually produced by hydrolyzing an appropriate chlorosilane or alkoxysilane by a method well known in the art.

The resinous copolymer of component (C) (that is, a copolymer having a three-dimensional network structure) has R ′ ₃ SiO _1/2 units and SiO ₂ units as main components. Here, R ′ is an unsubstituted or substituted monovalent hydrocarbon group, preferably having 1 to 10 carbon atoms, particularly 1 to 8 carbon atoms, and the monovalent hydrocarbon group represented by R ′ includes a methyl group, Alkyl groups such as ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, cyclohexyl group, octyl group, nonyl group, decyl group, phenyl group, tolyl group Aryl groups such as xylyl group and naphthyl group, aralkyl groups such as benzyl group, phenylethyl group and phenylpropyl group, vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, hexenyl group, cyclohexenyl group, octenyl Alkenyl groups such as groups, some or all of the hydrogen atoms of these groups are halogen atoms such as fluorine, bromine and chlorine, cyano groups, etc. Obtained by substituting, for example, chloromethyl group, chloropropyl group, bromoethyl group, trifluoropropyl group, cyanoethyl group and the like.

The resinous copolymer of component (C) may be composed only of the above R ′ ₃ SiO _1/2 units and SiO ₂ units, and if necessary, R ′ ₂ SiO units and R′SiO _{3 / 2} units (R 'above street of) the total amount of these with respect to the total copolymer mass, 50% or less, and preferably may comprise from 40% or less, R' ₃ SiO _1/2 The molar ratio [R ′ ₃ SiO _1/2 / SiO ₂ ] between the unit and SiO ₂ unit is preferably 0.5 to 1.5, particularly preferably 0.5 to 1.3. Even if this molar ratio is smaller than 0.5 or larger than 1.5, sufficient rubber hardness / strength cannot be obtained. Furthermore, the resinous copolymer of component (C) preferably has a content of alkenyl groups having at least two alkenyl groups in one molecule of 0.0001 mol / g or more, preferably 0.0001 to 0. 0.003 mol / g, more preferably in the range of 0.0002 to 0.002 mol / g. If the content of the alkenyl group is less than 0.0001 mol / g, sufficient rubber properties cannot be obtained, and if it is more than 0.003 mol / g, the hardness may be too high and the adhesive strength may decrease. is there.
The resinous copolymer may be a liquid (for example, 10 mPa · s or more, preferably 50 mPa · s or more) having fluidity at room temperature (25 ° C.) or a solid having no fluidity. . This resinous copolymer can be usually produced by hydrolyzing an appropriate chlorosilane or alkoxysilane by a method well known in the art.

  The content of the alkenyl group in the total of the resinous copolymer of the component (B) and the resinous copolymer of the component (C) is 0.00001 to 0 in terms of rubber properties and adhesiveness. It is preferably 0.002 mol / g, particularly 0.00005 to 0.001 mol / g.

  Here, the compounding amount of the component (A) is 10 to 75 parts by mass, particularly 20 to 70 parts by mass, the compounding amount of the component (B) is 20 to 70 parts by mass, particularly 25 to 60 parts by mass, (C) The compounding quantity of a component is 5-50 mass parts, especially 10-40 mass parts. If the amount of component (A) is too small, the rubber elasticity will be lost and brittle, and if it is too large, the tackiness and strength will be insufficient. When the amount of the component (B) is too small, sufficient tackiness cannot be obtained, and when it is too large, the tackiness is lowered and the rubber physical properties are significantly lowered. On the contrary, if the amount of the component (C) is too small, sufficient tackiness cannot be obtained, and if it is too much, the tackiness is lowered and the rubber physical properties are also significantly lowered.

The component (D) is an organohydrogenpolysiloxane having at least 2, preferably 3 or more hydrogen atoms (SiH groups) bonded to a silicon atom in one molecule, and the SiH group in the molecule is the above (A). The alkenyl group bonded to the silicon atom in the component, the component (B) and the component (C) is cross-linked by a hydrosilylation addition reaction, and acts as a curing agent for curing the composition. The organohydrogenpolysiloxane of component (D) has the following average composition formula (2)
R ² _b H _c SiO _{(4-bc) / 2} (2)
(Wherein R ² is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, b is 0.7 to 2.1, c is 0.001 to 1.0, and b + c is a positive number satisfying 0.8 to 3.0.)
And those having at least 2 (usually 2 to 200), preferably 3 to 100, more preferably 3 to 50 silicon atom-bonded hydrogen atoms in one molecule are suitably used. Here, examples of the monovalent hydrocarbon group for R ² include the same groups as those exemplified for R ¹ , but those having no aliphatic unsaturated group are preferred. Further, b is preferably 0.8 to 2.0, c is preferably 0.01 to 1.0, b + c is preferably 1.0 to 2.5, and the molecular structure of the organohydrogenpolysiloxane is: The structure may be any of linear, cyclic, branched, and three-dimensional network. In this case, the number of silicon atoms in one molecule (or the degree of polymerization) is preferably 2 to 300, particularly about 4 to 150 at room temperature (25 ° C.). In addition, the hydrogen atom couple | bonded with a silicon atom may be located in any of the molecular chain terminal and the middle of a molecular chain, and may be located in both.

Examples of the organohydrogenpolysiloxane of component (D) include trimethylsiloxy group-capped methylhydrogen polysiloxane at both ends, trimethylsiloxy group-capped dimethylsiloxane / methylhydrogensiloxane copolymer at both ends, and dimethylhydrogensiloxy groups at both ends. Blocked dimethylpolysiloxane, both ends dimethylhydrogensiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer, both ends trimethylsiloxy group-blocked methylhydrogensiloxane / diphenylsiloxane copolymer, both ends trimethylsiloxy group-blocked methylhydrogen diphenylsiloxane-dimethylsiloxane copolymers, copolymers consisting of (CH _{3) 2} HSiO _1/2 units and SiO _4/2 units, (CH _{3) 2} H iO _1/2 unit and the SiO _4/2 units (C ₆ H _5), such as copolymers comprising SiO _3/2 units and the like.

  The blending amount of the organohydrogenpolysiloxane of the component (D) is 0.5 to 30 parts by mass, particularly 0.8 to 20 parts per 100 parts by mass in total of the components (A), (B) and (C). Part by mass. If the blending amount is too small or too large, sufficient rubber strength cannot be obtained. The organohydrogenpolysiloxane of component (D) is bonded to the silicon atom in component (D) relative to the alkenyl group bonded to the silicon atom included in components (A), (B), and (C). The amount of hydrogen atoms (SiH groups) is blended in such an amount that the molar ratio is 0.32 to 0.75.

  As an addition reaction catalyst for component (E), platinum black, platinum chloride, chloroplatinic acid, a reaction product of chloroplatinic acid and a monohydric alcohol, a complex of chloroplatinic acid and olefins, chloroplatinic acid and vinyl Examples include complexes with siloxanes, platinum-based catalysts such as platinum bisacetoacetate, palladium-based catalysts, and rhodium-based catalysts. In addition, the addition amount of this addition reaction catalyst can be made into a catalyst amount, and 0.5-1,000 ppm with respect to the total amount of (A), (B), (C) component as a platinum group metal normally, It is about 1 to 500 ppm.

The hardness of the adhesive layer is smaller than the hardness of the base rubber, and is preferably in the range of 1-60 in terms of Asker C hardness, more preferably in the range of 2-55. If it is less than 1, the strength as a rubber may be inferior, and if it exceeds 60, the adhesiveness may decrease.
Moreover, based on JISZ0237, it adheres to glass (Nippon Sheet Glass Co., Ltd., FL2.0), and the adhesive force when performing a 180 ° peel test at a peeling speed of 300 mm / min is 0.5 to 10 N / 25 mm. In particular, 0.7 to 8 N / 25 mm is preferable. If it is less than 0.5 N / 25 mm, when sticking the adhesive layer to the desired part to be attached, the adhesive strength to the part to be attached is low, and there is a problem with sticking. Adhesion may be hindered.

  In addition to the above-described components, the composition for forming the base rubber layer and the adhesive layer includes, as necessary, other components such as fumed silica, precipitated silica, quartz powder, diatomaceous earth, and calcium carbonate. Fillers such as carbon black, conductive zinc white, conductive powder such as metal powder, and heat-resistant agents such as iron oxide and cerium oxide may be added, but in applications that require transparency It is not preferable. Furthermore, hydrosilylation reaction control agents such as nitrogen-containing compounds, acetylene compounds, phosphorus compounds, nitrile compounds, carboxylates, tin compounds, mercury compounds, sulfur compounds, internal mold release agents such as dimethyl silicone oil, adhesion imparting agents, thixotropes It is optional to add a property-imparting agent or the like. In addition, decorative articles such as beads and stones may be placed on the base rubber layer, and pictures and patterns may be printed.

  The thickness of the base rubber is 0.05 to 1 mm, preferably 0.1 to 0.7 mm. If the thickness is less than 0.05 mm, it may be insufficient for taking advantage of the elasticity of the sheet. If the thickness exceeds 1 mm, the weight increases, affecting the attachment, and may be disadvantageous in terms of cost. Further, the thickness of the adhesive layer is preferably in the range of 0.1 to 2 mm, more preferably in the range of 0.15 to 1.5 mm. If it is less than 0.1 mm, the surface unevenness of the part to be adhered to which the adhesive layer is adhered cannot be absorbed, and if it exceeds 2 mm, the rubber strength of the affixed surface depends on the adhesive layer and may cause rubber destruction.

  When forming the adhesive rubber sheet of the present invention, first, a base rubber is formed. In this case, the base rubber may be formed as a single layer using a rubber composition such as a silicone rubber composition, or may be formed as a composite layer with metal or various resins, for example, compression molding or injection molding. Integrate with other base materials by directly obtaining a sheet by injection molding, by molding a sheet on a metal substrate, resin substrate, resin film by insert molding, or by dipping, coating, calendar molding, screen printing, etc. For example, there is a method of obtaining a rubber sheet. In this case, calendar molding is preferable because it can be suitably used.

  The adhesive layer is laminated on the base rubber, but the base rubber is formed after the composition forming the base rubber is cured to form the base rubber. The composition to be formed is preferably calendered on a film of polyethylene terephthalate (PET) or the like and separated, and a composition that forms an adhesive layer in an unvulcanized state is preferably laminated.

  The composition for forming the adhesive layer is preferable because there is a method for obtaining a laminated sheet by a method such as dipping, coating, or screen printing on the composition for forming the base rubber layer, and coating molding can be suitably used. By simultaneously curing the base rubber composition and the adhesive layer composition, the adhesion at the lamination interface can be obtained. In addition, as these hardening conditions, the range of 10 second-1 hour is preferable at 80-250 degreeC. Further, after-curing may be performed at 120 to 250 ° C. for about 1 to 100 hours for the purpose of removing low molecular siloxane.

  The sticky rubber sheet of the present invention is used for sticking and decorating directly to the human body such as human skin and nails, specifically badges, emblems, seals, covers, earrings, earrings, characters It is used as a sticking sheet for human body decoration such as a sheet, nail polish, nail sheet, sun protection sheet, protective sheet, elastic sheet, cheering face or arm seal (national flag, team, etc.).

As shown in FIG. 1, the rubber sheet of the present invention usually has a cover film 3 such as a polyethylene terephthalate (PET) sheet laminated on the adhesive layer 2 so that the cover film 3 can be peeled off. It removes and the adhesion layer 2 is stuck on the required to-be-adhered part. In this case, if necessary, the rubber sheet of the present invention can be peeled off from the part to be stuck and re-sticked, and the reworkability is excellent.
2 shows an example in which the adhesive rubber sheet 10 of the present invention is used as a nail seal, and FIG. 3 shows an example in which it is used as a support seal for soccer or the like.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In the following examples, “part” means “part by mass” and “%” means “% by mass”.

[Example 1]
Millable dimethylsilicone rubber compound KE-571-U (manufactured by Shin-Etsu Chemical Co., Ltd., having a degree of polymerization of about 5,000) as a transparent uncrosslinked dimethylsilicone rubber compound in the base rubber layer And 40% or less of dry silica having a specific surface area of 200 m ² / g by BET method and 10% or less of silanol group-blocked dimethylsiloxane oligomer (silica dispersant) having a molecular weight of 700 or less in the compound. Addition (hydrosilylation) reaction system vulcanizing agent C-25A / B (manufactured by Shin-Etsu Chemical Co., Ltd.) 0.5 / 2.0 parts each to 100 parts (containing no phenyl group) The dimethyl silicone rubber composition kneaded with this roll is calendered and unvulcanized to a thickness of 0.2 mm on 100 μm embossed PET. Sheet to obtain a compound composition was separated out so as to obtain.

60 parts of dimethylpolysiloxane (1) having an average degree of polymerization of 300 blocked at both ends with dimethylvinylsiloxy groups on the adhesive layer, (CH ₃ ) ₃ SiO _1/2 units and SiO ₂ solid at room temperature (25 ° C.) Resinous copolymer consisting of ₂ units (2) [(CH ₃ ) ₃ SiO _1/2 units / SiO ₂ units (molar ratio) = 0.75] 40 parts, specific powder surface area of 110 m as fine powder silica ² parts / g of hydrophobized fumed silica (Nippon Aerosil Co., Ltd., R-972) 8 parts was placed in a planetary mixer, mixed for 30 minutes, and then passed once through three rolls. In 100 parts of this silicone rubber base, methyl hydrogen polysiloxane (3) having SiH groups in the molecular side chain (that is, on the siloxane unit in the middle of the molecular chain) as a crosslinking agent (polymerization degree 20, SiH group amount 0.0060 mol) / G) and 0.99 parts of ethynylcyclohexanol as a reaction control agent were added, and stirring was continued for 15 minutes to obtain a silicone rubber composition. This silicone rubber composition was mixed with 0.1 part of a platinum catalyst (Pt concentration 1%) to obtain a pressure-sensitive adhesive composition.

On the unvulcanized base rubber composition, using a comma coater, the pressure-sensitive adhesive composition is laminated and coated to a thickness of 0.5 mm, and then heated and cured in a heating furnace at 150 ° C. for 10 minutes to form two layers. A laminated cured sheet was obtained. The base rubber had a JIS-A hardness of 70, and the adhesive layer had an Asker C hardness of 40.
Table 1 shows the results obtained by peeling the substrate-side PET from the obtained laminated sheet and evaluating it by the following methods.
As a product, the PET attached to the base rubber layer side is peeled off, and a glossy 75 μm PET is attached to the adhesive layer side as shown in FIG.

[Comparative Example 1]
The base material layer is the same as in Example 1, fumed silica (Nippon Aerosil) having 100 parts of dimethylpolysiloxane (1) of Example 1 and a specific surface area of 200 m ² / g as measured by the BET method. 15 parts of Aerosil 200, 3 parts of hexamethyldisilazane and 1 part of water were kneaded at 150 ° C. for 2 hours. 1.26 parts of methylhydrogenpolysiloxane (3) having a SiH group in the molecular side chain of Example 1 as a crosslinking agent and 100 parts of ethynylcyclohexanol as a reaction control agent are added to 100 parts of this silicone rubber base. Then, stirring was continued for 15 minutes to obtain a silicone rubber composition. This silicone rubber composition was mixed with 0.1 part of a platinum catalyst (Pt concentration 1%) to obtain a pressure-sensitive adhesive composition.
A laminated cured sheet was obtained in the same manner as in Example 1. Table 1 shows the results obtained by peeling the substrate-side PET from the obtained laminated sheet and evaluating it by the following methods.

Each evaluation item / adhesiveness The obtained sheet was cut into a width of 25 mm and a length of 10 cm, and the glass FL2.0 manufactured by Nippon Sheet Glass Co., Ltd. was degreased with alcohol in accordance with JIS Z 0237 and air-dried 4 mm thick glass The adhesive layer side of the sheet was affixed to the plate, the glass and the adhesive layer were peeled off at 180 ° peel at a rate of 300 mm / min at room temperature, and the adhesive strength was measured.
・ Long-term sticking stability The above-prepared adhesive sheet is cut to a width of 25 mm and a length of 10 cm on a 4 mm thick glass substrate, the adhesive layer side is attached, and room temperature is 1 month at a humidity of 50% RH. After storage, the glass and the adhesive layer were peeled off at 180 ° peel at a rate of 300 mm / min at room temperature, and the adhesive strength was measured.
-Re-peelability On the 4 mm-thick glass substrate, the prepared adhesive sheet was cut to a width of 25 mm and a length of 10 cm, the adhesive layer side was attached, and stored for 1 month at room temperature and 50% RH humidity. Thereafter, the glass and the adhesive layer were peeled off at 180 ° peel at a rate of 300 mm / min at room temperature, and it was confirmed whether or not the adhesive component was transferred to the glass surface. Those where the adhesive component migrated were marked with ×, and those which did not migrate were marked with ○.
-Re-adhesiveness On the 4 mm-thick glass substrate, the prepared adhesive sheet is cut to a width of 25 mm and a length of 10 cm, the adhesive layer side is attached, peeled off, and then applied again to another glass substrate. Then, the glass and the adhesive layer were peeled off at 180 ° peel at a rate of 300 mm / min at room temperature, and the adhesive strength was measured.
-Elasticity against deformation When the laminated film was bent at 180 °, the presence or absence of damage to the laminated sheet was confirmed. Those with no change were marked with ○, and those with cracks / deformation were marked with ×.
-Human body skin adhesion retention The sheet | seat was cut into 3 cm x 2 cm, the adhesion layer side was stuck on human skin, and the adhesion state after one day was confirmed. Those that were not peeled were marked with ◯, and those that were peeled off were marked with ×.
-Human body nail adhesion retention The sheet was cut so that it could be affixed to a human nail, the adhesive layer side was attached, and the adhesion state after one day was confirmed. Those that were not peeled were marked with ◯, and those that were peeled off were marked with ×.

DESCRIPTION OF SYMBOLS 1 Base rubber 2 Adhesive layer 3 Cover film 10 Adhesive rubber sheet

Claims (8)

  A pressure-sensitive adhesive rubber sheet for decorating a human body, wherein a pressure-sensitive adhesive layer made of a pressure-sensitive silicone resin or gel is formed on a base rubber layer.   The adhesive rubber sheet according to claim 1, wherein the base rubber is formed from a silicone rubber having a hardness of JIS-A of 10 to 90. The adhesive layer is (A) an organopolysiloxane containing an alkenyl group bonded to at least two silicon atoms in one molecule: 10 to 75 parts by mass,
(B) R ₃ SiO _1/2 unit (wherein R is an unsubstituted or substituted monovalent hydrocarbon group) and SiO ₂ unit as main components, and the moles of R ₃ SiO _1/2 unit and SiO ₂ unit A resinous material in which the ratio [R ₃ SiO _1/2 / SiO ₂ ] is 0.5 to 1.5 and R does not contain an alkenyl group or the total amount is less than 0.0001 mol / g. Polymer: 20 to 70 parts by mass,
(C) R ′ ₃ SiO _1/2 unit (wherein R ′ is an unsubstituted or substituted monovalent hydrocarbon group) and SiO ₂ unit as main components, R ′ ₃ SiO _1/2 unit and SiO ₂ unit And the molar ratio [R ′ ₃ SiO _1/2 / SiO ₂ ] is 0.5 to 1.5, R ′ contains an alkenyl group, and the total amount thereof is 0.0001 mol / g or more. Combined: 5-50 parts by mass,
(D) Organohydrogenpolysiloxane containing at least two hydrogen atoms bonded to silicon atoms in one molecule: 0.5 to 30 with respect to 100 parts by mass in total of components (A), (B) and (C) The amount of hydrogen atoms bonded to the silicon atoms in the component (D) relative to the alkenyl groups bonded to the silicon atoms contained in the components (A), (B), and (C) is 0 parts by molar ratio. An amount of 32 to 0.75,
(E) Addition reaction catalyst: The adhesive rubber according to claim 1 or 2, wherein the cured product is formed from a cured product of an addition-curable silicone rubber composition having a surface adhesiveness, the catalyst containing a catalytic amount. Sheet.   The adhesive rubber sheet according to any one of claims 1 to 3, wherein the adhesive layer has a hardness lower than that of the base rubber and an Asker C hardness of 1 to 60.   The adhesive rubber sheet according to any one of claims 1 to 4, wherein the adhesive force of the adhesive layer to glass is 0.5 to 10 N / 25 mm.   The adhesive rubber sheet according to any one of claims 1 to 5, wherein the base rubber has a thickness of 0.05 to 1 mm, and the adhesive layer has a thickness of 0.1 to 2 mm.   It is a nail sheet, The adhesive rubber sheet of any one of Claims 1-6.   The pressure-sensitive adhesive rubber sheet according to any one of claims 1 to 6, which is a cheering face or an arm sticking sheet.

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